Magnetic Blocking Temperature Research Articles

Bis-Monophospholyl Dysprosium Cation Showing Magnetic Hysteresis at 48 K.

Single-molecule magnets (SMMs) have potential applications in high-density data storage, but magnetic relaxation times at elevated temperatures must be increased to make them practically useful. Bis-cyclopentadienyl lanthanide sandwich complexes have emerged as the leading candidates for SMMs that show magnetic memory at liquid nitrogen temperatures, but the relaxation mechanisms mediated by aromatic C5 rings have not been fully established. Here we synthesize a bis-monophospholyl dysprosium SMM [Dy(Dtp)2][Al{OC(CF3)3}4] (1, Dtp = {P(CtBuCMe)2}) by the treatment of in-situ-prepared “[Dy(Dtp)2(C3H5)]” with [HNEt3][Al{OC(CF3)3}4]. SQUID magnetometry reveals that 1 has an effective barrier to magnetization reversal of 1760 K (1223 cm–1) and magnetic hysteresis up to 48 K. Ab initio calculation of the spin dynamics reveals that transitions out of the ground state are slower in 1 than in the first reported dysprosocenium SMM, [Dy(Cpttt)2][B(C6F5)4] (Cpttt = C5H2tBu3-1,2,4); however, relaxation is faster in 1 overall due to the compression of electronic energies and to vibrational modes being brought on-resonance by the chemical and structural changes introduced by the bis-Dtp framework. With the preparation and analysis of 1, we are thus able to further refine our understanding of relaxation processes operating in bis-C5/C4P sandwich lanthanide SMMs, which is the necessary first step toward rationally achieving higher magnetic blocking temperatures in these systems in the future.

Variations in magnetic properties caused by size dispersion and particle aggregation on CoFe2O4

Size dispersion and particle aggregation are the key parameters that affect the magnetic properties at nanoscale due to interparticle interactions. However, few efforts have been devoted so far to understand how these parameters affect the magnetic properties of nanoparticles. Here, we experimentally demonstrate how the magnetic properties such as magnetic saturation (Ms), coercivity (Hc), Curie temperature (Tc), and blocking temperature (TB) of cobalt ferrite (CoFe2O4) nanoparticles having the same composition and near-average size are affected by size dispersion (σ) and aggregation. Cobalt ferrite nanoparticles of similar average sizes but different size dispersions and aggregations were fabricated through different synthesis routes. The results clearly demonstrate that just by reducing the size dispersion and aggregation, it is possible to modify the magnetic properties, e.g., achieving a superparamagnetic state of cobalt ferrite even under applied magnetic field as low as 100 Oe as indicated by ZFC measurements. The Stoner–Wohlfarth model with thermal agitation was used to simulate the blocking temperature of the different size dispersion and aggregation nanoparticles confirming that low size dispersion and non-aggregated particles have great influence to achieve the superparamagnetic state, especially for high coercivity materials such as cobalt ferrite.

High Blocking Temperature of Magnetization and Giant Coercivity in the Azafullerene Tb2 @C79 N with a Single-Electron Terbium-Terbium Bond.

The azafullerene Tb2@C79N is found to be a single‐molecule magnet with a high 100‐s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy‐axis single‐ion magnetic anisotropy are strongly coupled by the unpaired spin of the single‐electron Tb−Tb bond. Relaxation of magnetization in Tb2@C79N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τ QTM=16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped.

Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal\u2013metal bond

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln2@C80(CH2Ph) dimetallofullerenes (Ln2 = Y2, Gd2, Tb2, Dy2, Ho2, Er2, TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal–metal bonding orbital. Tb2@C80(CH2Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln2@C80(CH2Ph) is redox active, enabling electrochemical tuning of the magnetism.

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

The discovery of materials capable of storing magnetic information at the level of single molecules and even single atoms has fueled renewed interest in the slow magnetic relaxation properties of single-molecule magnets (SMMs). The lanthanide elements, especially dysprosium, continue to play a pivotal role in the development of potential nanoscale applications of SMMs, including, for example, in molecular spintronics and quantum computing. Aside from their fundamentally fascinating physics, the realization of functional materials based on SMMs requires significant scientific and technical challenges to be overcome. In particular, extremely low temperatures are needed to observe slow magnetic relaxation, and while many SMMs possess a measurable energy barrier to reversal of the magnetization ( Ueff), very few such materials display the important properties of magnetic hysteresis with remanence and coercivity. Werner-type coordination chemistry has been the dominant method used in the synthesis of lanthanide SMMs, and most of our knowledge and understanding of these materials is built on the many important contributions based on this approach. In contrast, lanthanide organometallic chemistry and lanthanide magnetochemistry have effectively evolved along separate lines, hence our goal was to promote a new direction in single-molecule magnetism by uniting the nonclassical organometallic synthetic approach with the traditionally distinct field of molecular magnetism. Over the last several years, our work on SMMs has focused on obtaining a detailed understanding of why magnetic materials based on the dysprosium metallocene cation building block {Cp2Dy}+ display slow magnetic relaxation. Specifically, we aspired to control the SMM properties using novel coordination chemistry in a way that hinges on key considerations, such as the strength and the symmetry of the crystal field. In establishing that the two cyclopentadienyl ligands combine to provide a strongly axial crystal field, we were able to propose a robust magneto-structural correlation for understanding the properties of dysprosium metallocene SMMs. In doing so, a blueprint was established that allows Ueff and the magnetic blocking temperature ( TB) to be improved in a well-defined way. Although experimental discoveries with SMMs occur more rapidly than quantitative theory can (currently) process and explain, a clear message emanating from the literature is that a combination of the two approaches is most effective. In this Account, we summarize the main findings from our own work on dysprosium metallocene SMMs, and consider them in the light of related experimental studies and theoretical interpretations of related materials reported by other protagonists. In doing so, we aim to contribute to the nascent and healthy debate on the nature of spin dynamics in SMMs and allied molecular nanomagnets, which will be crucial for the further advancement of this vibrant research field.

Antiferromagnetic Order in Epitaxial FeSe Films on SrTiO_{3}.

Single monolayer FeSe film grown on a Nb-doped SrTiO_{3}(001) substrate shows the highest superconducting transition temperature (T_{C}∼100 K) among the iron-based superconductors (iron pnictides), while the T_{C} value of bulk FeSe is only ∼8 K. Although bulk FeSe does not show antiferromagnetic order, calculations suggest that the parent FeSe/SrTiO_{3} films are antiferromagnetic. Experimentally, because of a lack of a direct probe, the magnetic state of FeSe/SrTiO_{3} films remains mysterious. Here, we report direct evidence of antiferromagnetic order in the parent FeSe/SrTiO_{3} films by the magnetic exchange bias effect measurements. The magnetic blocking temperature is ∼140 K for a single monolayer film. The antiferromagnetic order disappears after electron doping.

Monodisperse cobalt ferrite nanoparticles assembled on mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4): A magnetically recoverable nanocomposite for the photocatalytic degradation of organic dyes

Monodisperse cobalt ferrite (CoFe2O4) nanoparticles (NPs) were synthesized by thermal decomposition of metal precursors in the presence of surfactants and then assembled on mesoporous graphitic carbon nitride (mpg-C3N4) via sonication of two components in ethanol solution. The yielded nanocomposite, namely CoFe2O4/mpg-C3N4, were characterized by using many advanced analytical techniques (TEM, HR-SEM, EDX, XRD, BET, PPMS-VSM, UV–vis DRS and ICP-MS). The magnetic properties of the CoFe2O4/mpg-C3N4 nanocomposite were studied by using M-H and M-T loops and the magnetic saturation and blocking temperature of the nanocomposite were found to be 6.1 emu/g and 269 K, respectively. The nanocomposite were then tested in the photocatalytic degradation of Malachite Green (MG) and showed considerably high photocatalytic activity under UV-light irradiation. The effects of various key operating parameters comprising catalyst amount, initial dye concentration, pH and reaction time span for the degradation of MG dye were studied to optimize the reaction conditions. The maximum degradation efficiency (DE %) of 93.41% was obtained by using 0.08 g L−1 catalyst and 10 mg L−1 MG dye at pH 5 within 120 min reaction time. Besides MG, the photocatalytic degradation of several other organic dyes (methylene blue, acid orange 7 and rhodamine B) was also studied to exhibit the performance of CoFe2O4/mpg-C3N4 nanocomposite under the optimized conditions. The results revealed that the kinetic of dye removal process could be designated through the application of pseudo-first-order kinetic model. In addition to high photocatalytic activity, CoFe2O4/mpg-C3N4 nanocomposite could be magnetically recovered after the dye degradation and reused for consecutive five runs without a significant loss (nearly 17%) in their initial performance.

Strong carbon cage influence on the single molecule magnetism in Dy-Sc nitride clusterfullerenes.

Magnetic properties of endohedral metallofullerenes with nitride clusters DySc2N and Dy2ScN and different carbon cages are studied by SQUID magnetometry. All molecules behave as single molecule magnets (SMMs) and exhibit magnetic hysteresis. It is found that the blocking temperature of magnetization and relaxation times strongly depend on the fullerene cage, with the C80-Ih isomer offering the best SMM properties.

Giant coercivity and high magnetic blocking temperatures for N23\u2212 radical-bridged dilanthanide complexes upon ligand dissociation

Increasing the operating temperatures of single-molecule magnets—molecules that can retain magnetic polarization in the absence of an applied field—has potential implications toward information storage and computing, and may also inform the development of new bulk magnets. Progress toward these goals relies upon the development of synthetic chemistry enabling enhancement of the thermal barrier to reversal of the magnetic moment, while suppressing alternative relaxation processes. Herein, we show that pairing the axial magnetic anisotropy enforced by tetramethylcyclopentadienyl (CpMe4H) capping ligands with strong magnetic exchange coupling provided by an N23− radical bridging ligand results in a series of dilanthanide complexes exhibiting exceptionally large magnetic hysteresis loops that persist to high temperatures. Significantly, reducing the coordination number of the metal centers appears to increase axial magnetic anisotropy, giving rise to larger magnetic relaxation barriers and 100-s magnetic blocking temperatures of up to 20 K, as observed for the complex [K(crypt-222)][(CpMe4H2Tb)2(μ−{rm{N}}_2^ cdot)].

Constraining the Date of the Martian Dynamo Shutdown by Means of Crater Magnetization Signatures

AbstractMars is believed to have possessed a dynamo that ceased operating approximately 4 Ga ago, although the exact time is still under debate. The scope of this study is to constrain the possible timing of its cessation by studying the magnetization signatures of craters. The study uses the latest available model of the lithospheric magnetic field of Mars, which is based on Mars Global Surveyor data. We tackle the problem of nonuniqueness that characterizes the inversion of magnetic field data for the magnetization by inferring only the visible part of the magnetization, that is, the part of the magnetization that gives rise to the observed magnetic field. Further on, we demonstrate that a zero visible magnetization is a valid proxy for the entire magnetization being zero under the assumption of a magnetization distribution of induced geometry. This assumption holds for craters whose thermoremanent magnetization has not been significantly altered since its acquisition. Our results show that the dynamo shut off after the impacts that created the Acidalia and SE Elysium basins and before the crust within the Utopia basin cooled below its magnetic blocking temperature. Accounting for the age uncertainties in the dating of these craters, we estimate that the dynamo shut off at an N(300) crater retention age of 2.5–3.2 or an absolute model age of 4.12–4.14 Ga. Moreover, the Martian dynamo may have been weaker in its early stage, which if true implies that the driving mechanism of the Martian dynamo was not the same throughout its history.

Determination of Blocking Temperature in Magnetization and Mössbauer Time Scale: A Functional Form Approach

We studied the temperature dependence of the magnetization in an ensemble of monodomain nanoparticles both with dc magnetometry and Mossbauer spectroscopy. The analytical form of the temperature dependence is given by the complementary cumulative distribution function. This allows to determine the magnetization blocking temperatures of the sample by a fitting procedure. It is possible to calculate the Mossbauer blocking temperature by a single spectrum and the dc magnetization blocking temperature by two points of the thermoremanent magnetization curve, thus with a large reduction of the experimental work. The method may be used for particles with not too strong interactions, such happens in the Fe28 sample and not for samples with strong interactions as N30; it may be used for interparticle interaction energies up to 2 yJ and not for energies larger than 60 yJ. This method of analysis of the data should be used in the future work concerning the thermoremanent magnetization and Mossbauer spectra of magnet...

A Dysprosium Metallocene Single‐Molecule Magnet Functioning at the Axial Limit

AbstractAbstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] (1Dy Cpttt=1,2,4‐tri(tert‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth metallocenium cation [(Cpttt)2Dy]+ (2Dy) as a salt of the non‐coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low‐lying Kramers doublets correspond to a well‐defined MJ value, with no significant mixing even in the higher doublets.

A Dysprosium Metallocene Single‐Molecule Magnet Functioning at the Axial Limit

Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt )2 DyCl] (1Dy Cpttt =1,2,4-tri(tert-butyl)cyclopentadienide) by the triethylsilylium cation produces the first base-free rare-earth metallocenium cation [(Cpttt )2 Dy]+ (2Dy ) as a salt of the non-coordinating [B(C6 F5 )4 ]- anion. Magnetic measurements reveal that [2Dy ][B(C6 F5 )4 ] is an SMM with a record anisotropy barrier up to 1277 cm-1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low-lying Kramers doublets correspond to a well-defined MJ value, with no significant mixing even in the higher doublets.

Molecular Design for Single-molecule Magnetism of Lanthanide Complexes

This review highlights the effective design criteria for lanthanide single-molecule magnets, which show strong magnetic blocking temperature up to 60 K. Increase in the anisotropy barrier and decrease in the quantum magnetization are attainable by controlling the ligand field, local molecular symmetry related to the coordination geometry of the complex, and magnetic dipole–dipole interactions between the lanthanide ions. With recent advances in this field, a new 2-coordinate complex, which is predicted to show a blocking temperature of more than 77 K, is also introduced. The existence of a proton in the nitrogen atom of porphyrin ligands quenches the single-molecule magnet because of the destruction of the symmetry, which can be possibly overlooked because of the disorder of the position of the proton in the crystals.

Microstructural Features of Magnetic NiCoB Nanoparticles Addition to MgB2 Precursor Powders

Magnesium diboride (MgB2) is a superconductor characterized by interesting properties like rather high superconducting transition temperature Tc = 39 K, long coherence length and low anisotropy. In addition, it has a very simple crystal structure and low density. Those properties make the MgB2 an ideal candidate for a wide range of applications. To improve the electromagnetic properties of MgB2, magnetic nickel-cobalt-boron (NiCoB) nanoparticles (mean grain size 17 ± 3 nm) were added to Mg and B precursor powders and sintered at 650 °C, i.e. the temperature of MgB2 superconductor formation. The nearly spherical NiCoB nanoparticles, as-prepared by the chemical reduction of metallic salts, were amorphous according to previous study. The resulting MgB2 sample, formed after the sintering at 650 °C, was subjected to detailed microstructural analysis which included the application of various experimental methods: XRD, FE-SEM, EDS, elemental mapping, TEM and SAED. The methods confirmed the formation of new crystal CoNi phase (due to heat treatment at 650C), consisting of spherical nanoparticles (~ 6 nm) with tendency to spherical agglomerates formation. Those nanosized magnetic particles (characterized by the single domain magnetic structure and blocking temperature TB below room temperature), located at MgB2 grain boundaries, could serve as effective magnetic pinning centers in MgB2, thus improving its electromagnetic properties

A matter of minutes: Breccia dike paleomagnetism provides evidence for rapid crater modification

Abstract During an impact event, a crater’s transient structure adjusts gravitationally. Within medium-sized complex craters, a central uplift rises and collapses resulting in large-scale rotations of the target rock. Estimated crater modification rates from numerical models indicate that complex impact craters modify to a structurally stable state within tens of seconds to several minutes after excavation. However, there is little direct geologic evidence constraining these rates. We show how paleomagnetic measurements of lithic breccia dikes emplaced during crater excavation can be used to constrain the rate of crater modification within the central uplift of the ∼34-km-diameter Slate Islands impact structure, Ontario, Canada. The uniformity and linearity of paleomagnetic directions among the clasts and matrix of breccia dikes throughout the impact structure indicate that breccia dikes were frictionally heated above the magnetite Curie temperature (580 °C) during their emplacement and subsequently cooled in situ through magnetic blocking temperatures. The tight grouping of these paleomagnetic directions implies that these breccia dikes cooled and locked in magnetic remanence over a time interval in which the impact structure was not experiencing structural rotations and had already reached a stable state. Conductive cooling of the thinnest sampled breccia dike would have led to the recording of magnetic remanence approximately six minutes after emplacement. This constraint necessitates a stable crater structure only minutes after impact and presents a rare case in which a geological process can be resolved on such a short time scale.

Magnetic properties and spin dynamics of CoFeB–SiO2 multilayer granular heterostructures

It has been found that CoFeB–SiO2/C and CoFeB–SiO2/Bi2Te3 multilayer heterostructures with a cluster structure of CoFeB layers feature a long-range magnetic order in the entire temperature range from 2 to 300 K. At high temperatures (T = 300 K), CoFeB clusters exhibit magnetic properties characteristic of superparamagnets. At low temperatures (T = 5 K), clusters are ferromagnetic, and the easy magnetization axis is in the film plane. The temperature of the ferromagnetic-to-superparamagnetic state transition of clusters depends on a dielectric interlayer material: the use of Bi2Te3 instead of C as a spacer layer leads to an increase in the transition temperature by a factor of 4 and an increase in the magnetization blocking temperature of CoFeB clusters in a field of 100 Oe by a factor of 3.

Enhancing the magnetic blocking temperature and magnetic coercivity of {CrLn} single-molecule magnets via bridging ligand modification.

Replacing bridging benzoate ligands with 2-chloro-4,5-fluorobenzoate in a family of {CrLn} (Ln = Tb, Dy and Ho) single-molecule magnets result in significant improvements in magnetic relaxation time, magnetic hysteresis blocking temperature and magnetic coercivity.

Magnetic Properties and the Superatom Character of 13-Atom Platinum Nanoclusters

13-atom platinum nanoclusters have been synthesized quantitatively in the pores of the zeolites NaY and KL. They reveal highly interesting magnetic properties like high-spin states, a blocking temperature, and super-diamagnetism, depending heavily on the loading of chemisorbed hydrogen. Additionally, EPR active states are observed. All of these magnetic properties are understood best if one considers the near-spherical clusters as analogs of transition metal atoms with low-spin and high-spin states, and with delocalized molecular orbitals which have a structure similar to that of atomic orbitals. These clusters are, therefore, called superatoms, and it is their analogy with normal atoms which is in the focus of the present work, but further phenomena, like the observation of a magnetic blocking temperature and the possibility of superconductivity, are discussed.

Meta-Atom Behavior in Clusters Revealing Large Spin Ground States.

The field of single molecule magnetism remains predicated on super- and double exchange mechanisms to engender large spin ground states. An alternative approach to achieving high-spin architectures involves synthesizing weak-field clusters featuring close M-M interactions to produce a single valence orbital manifold. Population of this orbital manifold in accordance with Hund's rules could potentially yield thermally persistent high-spin ground states under which the valence electrons remain coupled. We now demonstrate this effect with a reduced hexanuclear iron cluster that achieves an S = 19/2 (χ(M)T ≈ 53 cm(3) K/mol) ground state that persists to 300 K, representing the largest spin ground state persistent to room temperature reported to date. The reduced cluster displays single molecule magnet behavior manifest in both variable-temperature zero-field (57)Fe Mössbauer and magnetometry with a spin reversal barrier of 42.5(8) cm(-1) and a magnetic blocking temperature of 2.9 K (0.059 K/min).